Process for preparing organometallic compounds

ABSTRACT

Compounds having a metal-to-carbon bond are prepared by using an electric arc to comminute metal and thus produce as the comminution progresses, metal in a highly reactive, finely divided form, which is caused to react as it is formed with a suitable organic reagent to form the desired product. This makes it possible to avoid the expense, the difficulties, and the dangers of working with a substantial quantity of finely divided metal in the making of such compounds. Using the invention, compounds having a metal-to-carbon bond are made more directly and inexpensively than in accordance with the practices known prior to the instant invention, and in some instances, such compounds are obtained in good yield, wherein with practices known prior to the instant invention, they were obtained in low yield, if at all.

[451 Apr. 29, 1975 PROCESS FOR PREPARING ORGANOMETALLIC COMPOUNDS [76] Inventor: John L. Lang, PO. Box 1242,

Midland, Mich. 48640 221 Filed: May 21,1973

211 App]. No.: 362,313

Related U.S. Application Data [60] Continuation of Set. No. 711,514, March 8, 1968, abandoned, which is a continuation of Ser. No. 595,372, Nov. 18, 1966, abandoned, which is a division of Ser. No. 134,256, Aug. 28, 1961, Pat. No. 3,299,026.

[52] U.S. Cl. 204/165; 204/59 R; 204/59 QM; 204/59 AM; 204/59 L; 204/164; 260/429 R; 260/429.9; 260/448; 260/448.2 R

[51] Int. Cl C07b29/06;C07f 5/00;C07 9/00 [58] Field of Search 204/164, 165, 59 OM, 59 L,

[56] References Cited UNITED STATES PATENTS 2,313,028 3/1943 Siegmann 250/546 X 3,299,026 1/1967 Lang 260/93] 3,323,954 6/1967 Goorissen 204/164 X OTHER PUBLICATIONS Organo-Metallic Compounds by Coates, pp. 29, 140, pub. by John Wiley and Sons, New York, 1960.

Primary Examiner-F. C. Edmundson [57] ABSTRACT Compounds having a metal-to-carbon bond are prepared by using an electric arc to comminute metal and thus produce as the comminution progresses, metal in a highly reactive, finely divided form, which is caused to react as it is formed with a suitable organic reagent to form the desired product. This makes it possible to avoid the expense, the difficulties, and the dangers of working with a substantial quantity of finely divided metal in the making of such compounds. Using the invention, compounds having a metal-to-carbon bond are made more directly and inexpensively than in accordance with the practices known prior to the instant invention, and in some instances, such compounds are obtained in good yield, wherein with practices known prior to the instant invention, they were obtained in low yield, if at all.

10 Claims, No Drawings PROCESS FOR PREPARING ORGANOMETALLIC COMPOUNDS CROSS-REFERENCES TO RELATED APPLICATIONS This application is in part a continuation of my earlier-filed copending application Ser. No. 71 1,514 filed Mar. 8, 1968, which is a continuation of my earlier application Ser. No. 595,372, filed Nov. 18, 1966. both now abandoned, which, in turn, is a division of my earlierfiled copending application Ser. No. 134,256, filed Aug. 28, 1961, now US. Pat. No. 3,299,026.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a process for producing compounds having a metal-to-carbon bond.

2. Description of the Prior Art Many hundreds of organometallic compounds (compounds having a metal-to-carbon bond) are known. Reference is made to the article on organometallic compounds in Organic Chemistry, Vol. 1, 2d edition, edited by John Gilman (Wiley and Sons, New York, 1943) and to the textbook by Geoffery Coates, Organometallic Compounds, 2d edition. published by Wiley and Sons, New York, 1961, for further detailed description of the many known compounds and the known methods of preparing them.

The invention will be better understood in the light of the following brief summary of the salient features of the prior art elaborated upon in the abovementioned references.

Practically every known metal has been shown to form organometallic compounds. There are, among others, the compounds that consist of a metal atom bonded to an appropriate number of alkyl or aryl groups (tetraethyl lead, triethyl aluminum, methyl lithium, etc.); the compounds that also contain a halogen atom bonded to the metal (phenylmagnesium bromide, n-butyl magnesium chloride); and the compounds that are Ir-bonded rather than U-bonded (ferrocene, Tr-dicyclopentadienyl manganese) as well as various derivatives of these. Within this vast number of compounds, there are certain ones that are known to have particular end uses (tetraethyl lead as an antiknock agent for gasoline, certain organotin compounds as biocides or rodent repellants). etc., and a great number of others that are useful in organic syntheses (especially the alkyl and aryl magnesium balides, which are also called Grignard reagents). The most important commercial organometallic compound is tetraethyl lead, and in the laboratory, the Grignard reagents are the most useful, though for many purposes they may be supplanted by organolithium compounds or organoaluminum compounds.

Methods of preparing organometallic compounds known prior to this invention have drawbacks, Syntheses that start with the metal itself usually require that the metal be obtained in pure form and then be put into a relatively finely divided state, avoiding oxidation. Frequently, there are the competing considerations that the metal should be very fine, so that it will not present so great a surface area that must be guarded against oxidation. There are other syntheses that start with, for example, the metal halide, but these generally require the use of another organometallic compound. which the metal halide reacts with, its metal replacing the metal of the other organometallic compound. The

drawback of such syntheses is that they are rather indirect or inefficient.

The chief commercial practice for making tetraethyl lead is disadvantageous in that it involves reacting ethyl chloride with a sodium-lead alloy, with only part of the lead being used in the reaction:

Sodium-lead alloys richer in sodium do not yield desirable results. The recovering and recycling of lead adds to the cost of the process.

The usual practice in making a Grignard reagent involves suspending magnesium turning in a solvent (usually diethyl ether, but tetrahydrofuran is necessary for some syntheses) and then carefully adding organic halide. The reaction is exothermic and starts slowly, usually after an induction period that is dependent upon the size and cleanliness of the magnesium particles. An explosion may result if halide is added too rapidly; halide additions are kept down to a rate that maintains the solvent at the boiling point, so that it vapors exclude water from the reaction zone, as is necessary because Grignard reagents react readily with water form the corresponding alcohol. The above-indicated laboratory practice is ill-suited for use on a large commercial scale, for a number of reasons. Obtaining the magnesium in finely divided form is itself rather a costly step, and then there must be faced either the drawback that the induction period of the reaction is quite lengthy (about 30-60 minutes or the drawback that special measures need to be taken to keep the finely divided magnesium from oxidizing. Practicing the method on a larger scale aggravates the problem of controlling the reaction adequately for example, adequate mixing is more difficult to obtain on a larger scale.

In the making of Grignard reagments on a laboratory scale, the use of diethyl ether has been usual. Unfavorable results have frequently been obtained when a different material, such as hydrocarbon fraction, is used as the solvent or suspending medium. Thus, examples tending to shown that a Grignard reagent may be prepared with the use of such other material will be understood by those skilled in the art to imply that a similar practice, but using diethyl ether or, if necessary, a higherboiling ether or tetrahydrofuran, would work at least as well, if not better.

US. Pat. No. 3,299,026, issued to the applicant Jan. 17, 1967, on application Ser. No. 134,256, filed Aug. 28, 1961, is prior art" with respect to this application to the extent that is must be found that the claims of this application are not for the same invention as the claims of that patent. In its claims 1 and 2, US. Pat. No. 3,299,026 defines the invention that solves the problem of obtaining metalloid reductant in a reactive dispersed form. The claimed solution to this very basic problem in chemistry is a process comprising the two steps of l) disposing a metalloid material within an inert fluid dispersing phase which will not react with the metalloid material... and (2) arcing a quantity of electrical energy through the metalloid material within the inert dispersing phase, the magnitude of the electrical energy being sufficient to disintegrate the metalloid material into finely divided unreacted form." Skilled chemists will understand that this is an exceedingly broad claim, covering an invention that has a very large number of possible uses. For one example, zinc metal arccomminuted in accordance with the invention might be reacted with an oxide or sulphide of a less electropositive metal to reduce the salt to the elemental metal. For another example, the colloidally dispersed metal. useful as a reductant, might not be used as such. but rather separated and dried of solvent under appropriate oxygen-free conditions to obtain a very finely divided metal power that would, quite obviously, have use in the field of powder metallurgy; it is implicit in the disclosure of the patent that a metal powder produced in this way is less costly than the same powder obtained by methods known prior to the invention defined in claims I and 2 of the patent. Still another example of the use of the invention of claims 1 and 2 of US. Pat. No. 3,299,026 is the use of the finely divided metal in the making of organometallic compounds in general and in the making of Grignard reagents in particular. Still another example of the use of the arc-comminuted metal of claims I and 2 of the patent is in the polymerization of such monomers as ethylene and styrene; it was known prior to the 026 patent that, for example, ethylene could be polymerized by using a Ziegler type catalyst comprising an aluminum alkyl and a heavymetal compound serving as a coreagent, and the 026 patent teaches that such polymerizations may be conducted by using a heavy-metal compound together with arc-comminuted metal as defined in claim 1, whether or not there is also present a compound such as an alkyl halide that will react with the arc-comminuted metal as it is formed to produce an organometallic reagent. Either the organometallic reagent or the finely divided metal itself will, when placed with a suitable heavymetal compound serving as a co-reagent and with a polymerizable monomer such as ethylene, propylene or styrene, will yield of a polymer. This invention, a route to additional polymers more convenient than that indicated by the prior art, is the subject of claims 3l2 of the 026 patent.

SUMMARY OF THE INVENTION Organometallic compounds are prepared by a novel process that is more convenient and safer than those known prior to the instant invention. Grignard reagents or other organometallic compounds are prepared directly from a corresponding metal, with the metal being placed in a finely divided state by arcing the metal with electricity in a dispersing phase at least a part of which is inert under the prevailing conditions, with the thusformed finely divided and highly reactive metal then being reacted with an organic reagent to produce the organometallic compound. The metal component of the organometallic compound may be used in bulk, instead of in the form of powders or the like that are easily oxidized, or even pyrophoric. By varying the amount of electricity supplied to the arc-comminution process, the rate formation of the arc-comminuted metal, and thus the rate of reaction, may be controlled. A wide variety of organometallic compounds based upon, among others, magnesium, aluminum, lead, tin, iron, and manganese, and encompassing organomctallic compounds of both the T-bonded and the vr-bonded type, may be thus prepared.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the invention, an organometallic compound is formed by arc-comminuting a suitable metal or metallike element in the presence of an inert LII dispersing phase and reacting the so-comminuted material with a suitable organic compound that supplies the organic moiety of the organometallic compound produced.

The metal or metal-like element used to produce a corresponding organometallic compound in accordance with this invention may be one of the following: lithium, rubidium, potassium, barium, strontium, calcium, sodium, magnesium, Zinc, manganese, beryllium, chromium, aluminum, tin, cadmium, titanium, gallium,

arsenic, bismuth, cobalt, nickel, iron, lead, silicon, mercury, phosphorus and antimony. Alloys of such materials, such as ferrosilicon amalgams, fused mixtures for carbides thereof may likewise be used. The metallic compound may be initially in either solid or liquid form.

Suitable solvents or fluid dispersing phases, for use in the preparation and use of products of this process are those Well known for use in the preparation of organometallic compounds made in accordance with conven tional methods. Some of the solvents that are satisfactory include hexane, heptane, mineral oil, Stoddard solvent, aromatic hydrocarbons such as benzene or the like, tertiary amines such as trialkyl amines or pyridine and homologs thereof, ethers including diethyl ether and cyclic ethers such as tetrahydrofuran or dioxane and their homologs, and other similar solvents. The criteria for suitable solvents is that l they are inert, or promote the formation and reaction of the organometallic material in its intended use, (2) they have a liquidus range in the vicinity of the desired operating temperatures of the reaction by means of which the organometallic compound is produced, and (3) they are less electrically conducting than the metal or metallike element itself. Space (e.g., vacuum or a partial vacuum) itself is an inert dispersing phase under certain conditions.

The electrical requirements for the arcing which disperses the metalloid component as a reactive species depends upon the electrode, its size, the distance separating the electrodes, the nature of the fluid dispersing phase, and other factors. Conditions required for various possible configurations have been studied in connection with are lighting, arc welding, and the like, and are well known in the art. For the sake of example, however, satisfactory results have been obtained with 22.2 grams of aluminum flakes cut from 0.005 inch thick aluminum sheet into pieces of approximately A X A; inch, suspended in 400 grams of hexane and arced by means of an electrical supply at llO volts, l5 amperes, 60 cycles per second alternating current, with a 600-watt resistor in series with the arc gap and a 1- microfared condenser in parallel therewith, the are gap being about ().I inch.

A suitable apparatus for use in carrying out the process of the invention on a small scale consists of a liter glass vessel fitted with sealed-in electrodes positioned so that the terminals are near the circumference and diametrically opposed on its circular flat bottom. The lid of the vessel is fitted with ports for the introduction of the metalloid reductant and solvents, as well as for the introduction of co-reagents, monomers, spargers, vacuum lines, etc., as needed. Beneath the vessel bottom is positioned a rotatable magnet whose poles move in a plane parallel with the vessel bottom, and the distance between which is slightly less than the distance between the aforementioned electrode termini, An-" other magnet, protected by a heatand corrosionresistant covering is placed on the vessel bottom as the actual stirring agitator. When the external magnet is turned by a suitable drive mechanism. the internal magnet turns and so stirs the contents of the vessel. This stirring action serves to make and break electrical pathways through the vessel contents by swirling the particles of the metal reductant into and out of juxtaposition during the application of electrical potential to the electrodes, causing the electrical arcing which serves to produce, as shown in the following examples, the product organometallic compounds in accordance with the process of the invention.

The sparger, inlet and other ports of the vessel are connected to their respective sources of inert gas, vacuum apparatus. solvent tanks, monomer tanks, monomer tanks, product receivers, etc., as required.

When it is desired to use a liquid metalloid, a particularly useful apparatus is one in which one electrode of the system for applying electrical energy is in an upper liquid reservoir, and the other is in the bottom pool of the liquid reservoir within the reaction vessel, with a drip-tip leading from the upper to the lower metalloid reservoir. The distance from the drip-tip to the surface of the bottom pool is adjusted, as by a leveling bulb, to match the requirements of the electrical potential for formation of an arc as the liquid metalloid drips into the lower reservoir.

An electrical system useful with small-scale apparatus has as its source a l l0-volt, 60 cycles-per-second alternating current source of IS amperes, connected to the electrodes through a 600-watt resistor in series with, and a l-microfarad capscitance in parallel with, said electrodes. Suitable apparatus of the type described above is shown, for example, in the aforesaid copending application Ser. No. 134,256, filed Aug. 28. I96], now U.S. Pat. No. 3,299.026.

Following or simultaneous with the formation of an arc-comminuted metal in accordance with the procedure indicated above, there is reaction of the arccomminuted metal with an organic co-reactant, to form an organometallic compound. Organic co-reactants useful in the formation of organometallic compounds by the process of this invention are very numerous, and they include, for example, the sterically unhindered and polarizably inclined organic chlorides, bromides, iodides, and equivalent materials. A partial list of typical compounds includes n-butyl chloride, n-butyl bromide, cyclohexyl chloride, bromobenzene, chlorotoluene, methyl iodide, and their homologs.

Compounds containing available and active multiplebonded carbon-go-carbon bonds may also be used to provide the organic moiety of the organometallic compound. Examples of such compounds are ethylene, propylene, butadiene, acetylene, and their homologs. When using such materials, hydrogen may also be added in certain cases. For example, in the making of lead tetraethyl, ethylene and hydrogen may be added to arccomminuted lead. Similarly, compounds having multiple unsaturation which confers aromatic" character can be used in the preparation of organometallic species by this invention. Organomstallic compounds of this type are exemplified by materials produced by the reaction of arc-comminuted' metal with benzene, naphthalene, oz-methyl styrene tetramer, cycclopentadiene, borazole, and their homologs and equivalents. In many instances, the organometallic compounds produced with the use of such aromatic materials are of the 'rr-bonded type typified by ferrocene and dicyclopentadienyl manganese. Other organometallic complex products so derived are typified by the initiating species of the so-called Living Polymer polymerizations elucidated by M. Swarc.

In this manner, there is produced an organometallic compound which, as is known to those skilled in the art (see Gilman, Organic chemistry, 2nd edition, 1943, pages 489580) may have the formula where R is an organic radical and M is an atom of a metalloid element selected from the list of metal or metal-like elements given above, and w is the valency of M or the formula RUMZII y nrmmoml'mllir where R is an organic radical, M is an atom ofa metalloid element selected from the list of metal or metallike elements given above, Z is a cation, y is a number at least I and not exceeding n, and n is a number not exceeding the maximum coordinate covalence of the atom M.

The organometallic compounds so produced can be used in various reactions such as the so-called Grignard, Wurtz-Fittig, Frankland, etc. reactions, as well as in may so-called catalyzed" reactions, or in polymerizations such as the metal-initiated and organometallic compound-initiated stereo-polymerizations of conjugated l,3-dienes, the Swarc sodium-naphthaleneinitiated living polymer procedure, as well as in interconversion reactions to form other organometallic compounds, or the like. Lead tetraethyl may be used as an antiknock agent for gasoline, and various organotin compounds are known as biocides. Grignard reagents may be used to form alcohols, acids or hydrocarbons, in accordance with procedures of organic synthesis well known to those skilled in the art.

From the foregoing teachings, it will be understood that lead tetraethyl may be manufactured by reacting arccomminuted lead with a gaseous mixture of hydrogen and ethylene. In doing this, it will be convenient to use gasoline as the solvent or fluid dispersing medium, thus producing immediately a concentrate material having lead tetraethyl dissolved therein and being miscible with unleaded gasoline stock in appropriate proportions to upgrade its antiknock characteristics to a desired extent. This procedure is remarkably more direct and efficient than the process now in common commercial practice for making and using lead tetraethyl.

Many modifications of the procedure are possible within the scope of the invention. Special conditions, such as specific-gravity relationships, may dictate changes in operation. For example, when lithium metal is used with hexane as the dispersing phase, with the intention that it be reacted with n-butyl bromide to make the species for use of polymerization of butadiene, it was found that use of lithium in the form of rods was preferred, because when lithium is used in chip or flake form, the lithium (specific gravity of 0.53 at 20C) floated on the hexae (specific gravity of 0.65 at 20C), even before the n-butyl bromide (specific gravity of 1.279 at 20C) was added.

The following examples are given merely as directed for carrying out certain specific preparations, in order that those skilled in the art may be guided while applying the process using other desired materials. These illustrative examples are not to be construed in any way as limiting the invention.

EXAMPLE 1 Into the reactor, there were placed 12.0 grams of magneisum chips, 5 milliliters of chlorobenzene, 300 grams of Stoddard Solvent 190-205 (a proprietary name for a hydrocarbon fraction), and l milliliter of pyridine. A two-inch agitator of magnetizable material. rotated by an external magnet, was used as a stirring bar. The vessel was then purged with dry argon for a time sufficient to displace all the other gases from the reactor. The electrical arcing current used was 110 volts alternating current, 60 cycles per second, with a 600-watt resistor in series with the arc and a 1 microfarad condenser in parallel with the arc. The are gap between the electrodes was about 1/16 inch. After arcing for one hour, the agitation, inert gas flow, and current were stopped. At this point, the reaction vessel contained phenyl magnesium chloride, a Grignard reagent. This was established by carbonating the contents of the reactor with solid carbon dioxide snow and then adding 100 milliliters of de-ionized water and 50 milliliters of concentrated 357: hydrochloric acid. The oil and water layers were separated and the water layer was treated with barium dichloride solution until all the acid was precipitated. As those skilled in the art will understand. the precipitate was barium benzoate. This barium salt was washed and dried; it weighed 4.1 grams, and it was then placed in 100 milliliters of deionized water and slurried therein. Sulfuric acid was added to liberate the acid, which was then recrystallized and dried. There was thus obtained 1.8 grams of a material having a melting point of 121C, which agrees closely with the published melting point of benzoic acid.

EXAMPLE ll Into a reaction vessel, there were charged 22.5 grams of aluminum flakes cut from about 0.125 millimeter thick into rectangular pieces of about 7 millimeters by 4 millimeters and also 5 milliliters of n-butyl chloride and 400 grams of light paraffin oil. After closure. the inlet lines were purged, and the reaction vessel was further purged with argon for twenty minutes. Then agitation was begun, and electricity was applied as described above, with the arcing being continued for about twenty minutes. A mixture of organoaluminum compounds was produced. lt is to be understood that aluminum exhibits different valency states, so that the product comprises various n-butyl aluminum chlorides.

These organoaluminum compounds may be used in the same manner as materials conventionally prepared for the polymerization of alpha-olefins, such as ethylene, in accordance with the Ziegler process, namely, by admixing them with titanium tetrachloride.

EXAMPLE 111 Example 11 was repeated, except that 0.5 milliliter of bromobenzene was added, instead of n-butyl chloride, with the bromobenze being added before arcing commenced. Arcing was continued for 45 minutes, and then titanium tetrachloride, 0.1 milliliter was added, producing a mixture suitable to catalyze the polymerization of an alpha-olefin. Here the products are mixed phenyl aluminum chlorides.

EXAMPLES IV A reaction vessel was charged with about 400 grams of dry heptane, 27 grams of titanium metal turnings (about 8 mesh), and 5.0 milliliters of t-butyl chloride. Argon was used to purge the reactor until all contaminating gases were removed. The agitator was started, and the electrical supply was turned on to initiate arcing. After arcing for 30 minutes, 1.0 milliliter of titanium tetrachloride was added, and the dispersion contained in the reactor became brownish black in color. Arcing was continued for an additional 15 minutes, yielding t-butyl titanium chloride. Ethylene was then introduced, and this caused formation of a light brown polymer slurry, from which the polymer was recovered.

since tertiary butyl chloride will not itself reduce titanium chloride in the manner just described, the above example shows the formation of an organometallic compound which is indeed capable of reducing the titanium tetrachloride later added. thus producing a catalytically active material.

EXAMPLE V A vessel was charged with 30 grams of -l0 mesh ferrosilicon, 300 grams of dry hexane, 5.0 grams of pyridine, 1.6 grams of bromobenzene, and 2.0 grams of anhydrous magnesium chloride. The atmosphere in the vessel was displaced by nitrogen, and agitation and areing were begun and maintained in the vessel as described above in Example 1. Arcing was continued for b l-l/2 hours.

An organometallic material, i.e., a type of so-called Grignard reagent, was thereby produced, as detected by carrying out a reaction typical of such Grignard reagent, namely, the reaction with carbon dioxide to form a carboxylic acid. Upon addition of an excess of carbon dioxide snow to the contents of the reactor and subsequent acidification by the addition of 500 milliliters of dilute (10%) hydrochloric acid, the benzoic acid thus produced was recovered. The yield was 0.92 gram, and the melting point was 120.6-121.2C.

EXAMPLE Vl lnto apparatus such as that described above for the handling of liquid metals, mercury was placed in both the upper reservoir and the bottom of the vessel. Dry hexane, which had been distilled from sodium, was charged into the vessel, which was then sparged with argon. An electrical potential of 1 10 volts was applied to the electrodes, and the drop tube was adjusted vertically to achieve arcing; the plug-cock was adjusted so that there was a stream of droplets slowly dripping from the tip of the tube. When proper vertical adjustment was made, an are formed and was broken every time a drop fell from the tip of the drop tube. This arcing under hexane produced a dense gray cloud of dispersed mercury in the solvent. To this there was added 1 milliliter of benzyl chloride, and arcing was continued at a rate of two drops per second for a period of 30 minutes.

The arcing was stopped and the hexane solution was petroleum ether and treated with sodium wire to convert the benzyl mercury chloride to dibenzyl mercury. exhibiting a melting point of 1 105C.

EXAMPLE Vll Lithium metal was pressed into rod form and two rods were positioned in the reactor so that an electric arc could be struck and maintained between them in the protected region provided by the inert dispersing medium, which in this example was dried hexane. Into 250 milliliters of the dried hexane was added milliliters of n-butyl bromide, and arcing begun and continued for minutes. Since n-butyl lithium is known to be difficult to isolate and is purified by slow evaporation rather than by a true distillation, the existence thereof was shown by reaction with a excess of benzyl chloride, which is known to couple by reaction, forming a yellow compound, benzyl lithium, as intermediate. This reaction was carried out, and the final product, 1,2-diphenyl ethane exhibited the proper melting point of 5 l52C.

Other reactive metals of low specific gravity may be used to form organometallic compounds in the same manner. Such metals include sodium, potassium, calcium, and barium. The organometallic compounds of these elements are non-volatile, high-melting solids which can be characterized only by their reactions, like the Grignard reagent of Example 1.

EXAMPLE Vlll Into a reactor as described above, there were placed 250 grams of hexane dried with Type 4A molecular sieves, 22.0 grams of granular (about minus /z inch) antimony metal, and the magnetic stirring bar. The system was purged for minutes with dried nitrogen, and an atmosphere of nitrogen was maintained in the vessel throughout the remainder of the experiment. Then 15.0 grams of bromobenzene were added by syringe, and the electric arc current was turned on, so as to maintain arcing conditions for about 1 hour. The arcing was stopped, and the contents of the reactor were filtered to remove the excess metal.

The hexane was removed under vacuum, and a powder product was obtained, which had a melting point of 84.5-85C, corresponding to that of 86C for the known diphenyl antimony bromide.

EXAMPLE lX Example Vlll was repeated, except that bismuth metal sticks were used in place of the antimony. There was obtained a product that melted at 157.5C, corresponding to the known melting point of diphenyl bismuth bromide.

EXAMPLE X There were placed in a reaction vessel 250 milliliters of hexane dried byy Type 4A molecular sieves," 30.0 grams of 60 mesh manganese metal powder, and a glass-covered magnetic stirring bar. The reaction vessel was purged for 30 minutes with dried nitrogen, which was also used to maintain an inert atmosphere in the reactor thoughout the course of the experiment. After the initial purging period, 13.1 grams of cyclopentadiene were introduced, and an electric arcing of the maganese metal was conducted for 1 hour. The mixture of the thus-produced biscyclopentadienyl manganese and manganese metal was separated without exposure to air, and was then vacuum sublimed to obtain 0.12

gram of dark brown powder. This undergoes the typical color change to pink at 158C, and melts at the temperature 173C, that is characteristic of biscyclopentadienyl magnanese.

EXAMPLE X1 EXAMPLE Xll Into a l-liter glass reactor as described above, there were placed 250 milliliters of dry Stoddard Solvent -205, 15 grams of small pieces of mossy zinc (minus inch), and twoinch glass-covered magnetic stirring bar. The vessel was purged with argon for /2 hour, and an argon atmosphere was maintained throughout the experiment. After purging, l0 milliliters of chlorobenzene were added, the electrical system was connected. and arcing conditions were maintained in the vessel for 30 minutes. The excess zinc was removed by filtration, and a crystalline product was obtained. All the necessary isolation and characterization procedures were carried out in a dry box. The product melted at 106l 07C, corresponding to the known melting point of diphenyl zinc.

EXAMPLE Xlll Example Xll was repeated, except that cadmium metal was used in place of zinc and bromobenzene was used in place of chlorobenzene. The reaction gave diphenyl cadmium, melting point 172-l 73C.

EXAMPLE XlV Example Xll was repeated, except that tin metal was used in place of zinc and ethyl bromide was used in place of chlorobenzene. There was thus obtained a mixture of products, from which diethyl tin bromide, having the proper melting point of 63C, was isolated.

EXAMPLE XV Into a reactor as described above, there were placed 400 milliliters of hexane dried by contacting for 16 hours, using a horizontal rotary mixer, with Type 4A molecular sieves, a commercial synthetic zeolite drying agent, and 24.0 grams of silicon metal, along with a three-inch glass-covered magnetic stirring bar. The vessel was purged with nitrogen for /2 hour, and then 12.7 grams (0.1 mol) of benzyl chloride was added. The nitrogen atmosphere was maintained while the electric current was turned on, and arching conditions were maintained for 45 minutes. The hexane became gray during the reaction period. After this time, the reaction contents were removed, the unreated silicon (21.9 grams) was removed by filtration, and a 25- milliliter aliquot of the filtrate was mixed with water and allowed to evaporate. Upon standing overnight, a polymeric silicone resin was formed. The remainder of the filtrate was worked up by being washed under inert atmosphere, and there was obtained a crystalline product having the melting point of 49.5-5l.0C, corresponding to the known melting point of dibenzyl silicon dichloride.

EXAMPLE XVI Into the apparatus as described above, there were placed 250 milliliters of hexane dried by distillation from sodium, and 87 grams of V8 inch X Vs inch pieces of lead out from 8-mil sheet. The reactor was purged with dry argon for /2 hour, and 53 grams of bromobenzene were added by syringe. The electric current was turned on. and arcing was continued for 1 hour. with argon being used to provide an inert atmosphere in the vessel throughout this period. Then the reactor contents were removed, and the product was separated by evaporation and filtration. There were recovered 2.6 grams of white, crystalline triphenyl lead bromide. melting point 165C. The recovered lead metal foil weighed 85.2 grams.

EXAMPLE XVlI Two iron rods one-quarter inch in diameter were positioned in the reactor as described in Exampale V11. Magnetic stirring cannot be used easily with magnetic materials such as iron or nickel. The inert phase in this example was 250 milliliters of Stoddard Solvent 190-205. The reactor war purged for 0.5 hour with dried nitrogen. and 13.1 grams of cyclopentadiene were added, and arcing was conducted under nitrogen. Within a few minutes, the orange color of ferrocene bis-cyclopentadienyl iron) was noted. Arcing was continued for 1 hour. The reactor contents were filtered, and 0.6 gram of ferrocene was recovered, exhibiting a melting point of 173C.

EXAMPLE XVlll zinc. manganese. beryllium. mercury, aluminum, tin. cadmium, titanium, gallium, arsenic. bismuth, chromium. cobalt, vandium. nickel. iron, lead, antimony, silicon, and phosphorus with at least one reagent selected from the group consisting of sterically unhindered and polarizably inclined organic halides and compounds containing available and active multiple bonded carbon bonds, which comprises disposing an electrically conductive body containing said element in a form selected from the group consisting of elemental metal, a solid mixture, an amalgam, an intermetallic compound, fused mixtures, and carbides thereof, within a non-interfering fluid dispersing phase, arcing said electrically conductive body by passing a quantity of electricity therethrough within said non-interfering dispersing phase, the magnitude of the electrical energy being sufficient to progressively disintegrate said body into finely divided form, and reacting said finely divided element with said reagent.

2. A process as defined in claim 1, characterized in that said element is magnesium, and in that said reagent is a sterically unhindered and polarizably inclined organic halide.

3. A process as defined in claim 1, characterized in that said element is aluminum. and in that an olefin and hydrogen are used as reagents.

4. A process as defined in claim 1, characterized in that said element is lead.

5. A process as defined in claim 1, characterized in that said element is lithium.

6. A process as defined in claim 1, characterized in that said element is sodium.

7. A process as defined in claim 1, characterized in that said element is silicon.

8. A process as defined in claim 1, characterized in that said element is phosphorus.

9. A process as defined in claim 1, characterized in that said element is zinc.

10. A process as defined in claim 1, characterized in that said element is tin.

. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,880,7Q-5 Dated April 29, 1975 Inventor(s) John Lang It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

olumn 1, line 61 Delete "not" and insert "now" Column 2, line 13 The word "turning should read "turninos" In Column 2, line 24 Delete the word "alcohol." and insert the ord "alkane".

' In Column 6, line 21 Delete the words "a cation" and insert the ords "an anion".

In Colurm 6, line 64 The word "hexae" should read "hexane" In Column 7, line 8 "maqneisum" should read "r aonesium".

In Column 8, line 18 The word "since" should be capitalized to read "Since".

FORM PO- uscoMM-oc 60376-P69 U.S. GOVERNMENT PRINTING OFFICE: a 9 93 O Page 2 UNITED STATES PATENT OFFICE Patent No. 5,88O7L5 Dated April 1975 Inventor(s) John L. Lang It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

elumn 1, line 16 The rissi w character at the hec inninc 0* the line should he inserter so as to read "1/ inch) In Column 10, line 16 The wissino; hyphen should he inserted so as to read two inch In Column 11, line 21 z The word "var" should he made to read "was".

In Claim 1, Column 11, -ine 38 The word "foor" should read "for".

Engnecl and Scaled this twenty-first Day Of October 1975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner u/Patents and Trademarks F ORM PO-10SO (10-69) USCOMM-DC 60376-P69 U.S GOVERNMENT PRINTING OFFICE: a 93 o 

1. A PROCESS FOOR PRODUCING AN ORGANOMETALLIC COMPOUND BY REACTION OF ATOMS OF AN ELEMENT SELECTED FROM THE GROUP CONSISTING OF LITHIUM, RUBIDIUM, POTASSIUM, BARIUM, STRONTIUM, CALCIUM, SODIUM, MAGNESIUM, ZINC, MANGANESE, BERYLLIUM, MERCURY, ALUMINUM, TIN, CADMIUM, TITANIUM, GALLIUM, ARSENIC, BISMUTH, CHROMIUM, COBALT VANDIUM, NICKEL, IRON, LEAD, ANTIMONY, SLICON, AND PHOSPHORUS WITH AT LEAST ONE REAGENT SELECTED FROM THE GROUP CONSISTING OF STERICALLY UNHINDERED AND POLARIZABLY INCLINED ORGANIC HALIDES AND COMPOUNDS CONTAINING AVAILZBLE AND ACTIVE MULTIPLE BONDED CARBON BONDS, WHICH COMPRISES DISPOSING AN ELECTRICALLY CONDUCTIVE BODY CONTAINING SAID ELEMENT IN A FORM SELECTED FROM THE GROUP CONSISTING OF ELEMENTAL METAL, A SOLID MIXTURE, AN AMALGAM, AN INTERMETALLIC COMPOUND, FUSED MIXTURES, AND CARBIDES THEREOF, WITHIN A NON-INTERFERING FLUID DISPERSING PHASE, ARCING SAID ELECTRICALLY CONDUCTIVE BODY BY PASSING A QUANTITY OF ELECTRICITY THERETHROUGH WITHIN SAID NON-INTERFERING DISPERSING PHASE, THE MAGNITUDE OF THE ELECTRICAL ENERGY BEING SUFFICIENT TO PROGRESSIVELY DISINTEGRATE SAID BODY INTO FINELY DIVIDED FORM, AND REACTING SAID FINELY DIVIDED ELEMENT WITH SAID REAGENT.
 2. A process as defined in claim 1, characterized in that said element is magnesium, and in that said reagent is a sterically unhindered and polarizably inclined organic halide.
 3. A process as defined in claim 1, characterized in that said element is aluminum, and in that an olefin and hydrogen are used as reagents.
 4. A process as defined in claim 1, characterized in that said element is lead.
 5. A process as defined in claim 1, characterized in that said element is lithium.
 6. A process as defined in claim 1, characterized in that said element is sodium.
 7. A process as defined in claim 1, characterized in that said element is silicon.
 8. A process as defined in claim 1, characterized in that said element is phosphorus.
 9. A process as defined in claim 1, characterized in that said element is zinc.
 10. A process as defined in claim 1, characterized in that said element is tin. 